There is a continuing search for materials having desirable fragrance properties. Such materials are sought either to replace costly natural materials or to provide new fragrances or perfume types which have not heretofore been available. Especially desirable qualities for substances having interesting petitgrain-type fragrances and lavender-type fragrances are stability and persistence, particularly in a wide variety of perfumed articles (e.g. soaps, detergents and powders), perfume compositions and colognes, ease of manufacture, and intensity of aroma.
Prior to this last decade, it was the general opinion among those skilled in the art that compounds containing the mercapto or --SH moiety were not desirable for use in conjunction with fragrance materials and perfumed articles, such as soaps, detergents and powders. However, within the last decade such compounds have been ascertained to be highly useful in perfumery. Thus, for example, Canadian Pat. No. 983,050, issued on Feb. 3, 1976 teaches that 3,7-dimethyl-octa-2,6-dienyl-mercaptan (thiogeraniol) of the formula: ##STR3## is used in making up a "synthetic buchu leaf oil" and imparts to a lavender type composition a greener and more herbal fragrance. USSR Pat. No. 345,677 teaches that para-menthane-8-thiol-3-one is useful as a synthetic blackcurrent flavoring for foodstuffs. This compound has the structure: ##STR4## German Offenlegungschrift Pat. No. 2,316,456, published on Oct. 11, 1973 discloses the use of certain thio alcohols or their corresponding esters in perfumery and in perfumed articles, such as detergents, cosmetics and waxes. Such mercapto alcohols having the generic structure: ##STR5## wherein R.sub.1 is a hydrocarbon moiety having from 1 up to 7 carbon atoms and R.sub.2 is one of hydrogen, methyl or ethyl.
However, no disclosure of the prior art contains a teaching to the effect that compounds having the generic structure: ##STR6## wherein R is one of ethyl, 1-propyl, 2-propyl or 1-butyl; and X is one of: ##STR7## has the ability to create an intense grapefruit, and/or green fruity and/or concord grape and/or buchu leaf oil-like aromas as is carried out in the instant invention. Furthermore, other mercaptans in the prior art, which are shown to be useful in perfumery are indicated to have berry or floral like fragrances, e.g. ionone and irone derivatives having the structure: ##STR8## as disclosed in British Pat. No. 1,327,320, published on Aug. 22, 1973 (wherein one of the dashed lines represents a double bond).
Certain .alpha.-oxy(oxo)mercaptans are disclosed in the prior art, but their uses in perfumery, in perfumed articles or in colognes are not disclosed. Thus, U.S. Pat. No. 3,773,524, issued on Nov. 20, 1973, discloses the use of .alpha.-ketothiols of the formula: ##STR9## wherein R.sub.1 is methyl or ethyl; and R.sub.2 and R.sub.3 are hydrogen, methyl or ethyl to alter the meat flavor and aroma of foodstuffs. U.S. Pat. No. 3,892,878, issued on July 1, 1975, discloses the use of certain .alpha.-hydroxymercaptoalkanes to alter the flavor of foodstuffs, for example, 2-mercapto-3-butanol used in meat flavors. The genus disclosed by U.S. Pat. No. 3,892,878 as follows: ##STR10## wherein X is oxygen or sulfur, n is 0 or 1, R.sub.1 -R.sub.7 are the same or different and each is hydrogen or lower alkyl of 1-4 carbon atoms, a and b are the same or different and each represents an integer of from 0 to 10 when n is 0 and when n is 1, a and b are the same or different and each represents an integer of from 1 to 10. 3-mercaptoheptanone-4 is disclosed per se in U.S. Pat. No. 2,888,487, issued on May 26, 1959. 3-mercapto-2,6-dimethyl-heptan-4-one is disclosed in Chem. Abstracts 6478 (d) Vol. 62, 1965 (abstract of Asinger, Diem and Schaefer, Monatsch. Chem. 95 (4-5), 1335-54 (1964). Beilstein E-IV-1 discloses 2-mercapto-2,4-dimethyl-pentan-3-one at page 4039, 1-mercapto-octan-2-one at page 4040, and 1-mercapto-nonan-2-one at page 4052 and 1-mercapto-undecan-2-one at page 4060.